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Ionic Crystal Structures02:42

Ionic Crystal Structures

Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
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Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
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Fabrication and Optimization of Type II Silicon Clathrate Films
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Fabrication and Optimization of Type II Silicon Clathrate Films

Published on: October 14, 2025

Tin clathrates with the type II structure.

Marion C Schäfer1, Svilen Bobev

  • 1Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States.

Journal of the American Chemical Society
|January 19, 2013
PubMed
Summary

Researchers synthesized new tin clathrates with the type II structure, expanding the known family of these compounds. These novel materials were created using alkali and alkaline-earth metals to fill specific cages within the structure.

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Area of Science:

  • Materials Science
  • Solid State Chemistry
  • Inorganic Chemistry

Background:

  • Type II clathrates are cage-like structures with potential applications in thermoelectric materials.
  • Barium gallium tin (Ba-Ga-Sn) clathrates with the type II structure were previously limited to a single known composition.

Purpose of the Study:

  • To synthesize and characterize new members of the type II Ba-Ga-Sn clathrate family.
  • To explore the role of alkali and alkaline-earth metals in stabilizing these structures.

Main Methods:

  • High-temperature solid-state synthesis.
  • Single-crystal X-ray diffraction for structural determination.
  • Elemental analysis to confirm composition.

Main Results:

  • Discovery and synthesis of three new type II clathrates: Cs(8)Ba(16)Ga(39.7(3))Sn(96.3(3)), Rb(9.9(5))Ba(13.3(2))Ga(36.4(3))Sn(99.6(3)), and K(2.0(4))Ba(14.0(4))Ga(30.4(2))Sn(105.6(4)).
  • Demonstration that alkali and alkaline-earth metals can be incorporated into the cages of type II clathrates.
  • Detailed structural characterization of the novel compounds.

Conclusions:

  • The Ba-Ga-Sn type II clathrate family has been significantly expanded with the discovery of new cesium, rubidium, and potassium-containing members.
  • The selective filling of cages by alkali and alkaline-earth metals is a viable strategy for synthesizing new clathrate compounds.
  • These findings open avenues for exploring new materials with potentially tunable properties.